Water compatible energy curable compositions containing malemide derivatives

ABSTRACT

Active water compatible actinic radiation curable printing ink or coating compositions comprised of maleimide derivatives, water compatible resins and water, which are capable of curing at a practical intensity and energy level and a method for curing same.

[0001] This application is a Divisional of U.S. patent application Ser.No. 09/831,688, entitled “Water Compatible Energy Curable CompositionsContaining Maleimide Derivatives”, now pending.

BACKGROUND OF INVENTION

[0002] 1. Field of the Invention

[0003] The present invention relates to active water compatible energycurable compositions containing a maleimide derivative, useful forpreparing various coatings, printing inks, surface finishes, moldings,laminated plates, adhesives, and binders. More specifically, the presentinvention relates to active water compatible energy curablecompositions, which can be cured in the absence of a photoinitiator withan irradiation source of practical intensity and energy value.

[0004] 2. Description of Related Art

[0005] An active energy curable composition polymerized underirradiation of active energy such as thermal energy, ultraviolet light,visible light, and the like, has an advantage of being rapidly cured.Active energy curable compositions are widely used as paints, inks,adhesives, coatings, and the like. However, conventional ultravioletactive energy curable compositions cannot initiate polymerization aloneupon irradiation with an energy source; it is therefore necessary to usea photoinitiator. When photoinitiators are used in large quantities,curing progresses rapidly, which encourages the use of large quantitiesof photoinitiator.

[0006] Photoinitator compounds having an aromatic ring are used ingeneral because they effectively absorb ultraviolet light. However,these compounds cause problems such as the yellowing of the curedmaterials upon addition of heat or light. Moreover, low molecular weightenergy curable monomers and oligomers, commonly used as photoinitiatorsbecause of their solubility a property necessary to initiatephotopolymerization effectively, unfortunately have high vaporpressures. Therefore, they tend to give off unpleasant odors attemperatures ranging from room temperature to 150° C. Because infraredlight, for example, is generated from an ultraviolet energy source,active energy curable compositions are heated substantially upon contactwith such light sources. The heating problem is magnified when theultraviolet light lamps are arranged and used in a side-by-side fashion.The unpleasant odors given off from the photoinitiator result in anunhealthy working environment.

[0007] Unreacted or decomposed photoinitiators remain behind inconventional energy curable compositions even after exposure toirradiation by the active energy cure source. These unreacted ordecomposed photoinitiators cause problems such as changing the color ofthe cured film to yellow, unpleasant odors, and the like, when the curedfilm is exposed to heat or light. For example, when a material at hightemperature, such as a thermal head, contacts an active energy curablecomposition comprising photoinitiator, strong unpleasant odors are givenoff. Finally, when these cured compositions are contacted by water afterirradiation; unreacted photoinitiator is exuded; therefore causing theactive energy curable composition to be unsuitable for food packagingapplications.

[0008] In solving some of these problems, the prior art presents manyoptions. For instance, JP-A-58-89609 discloses an energy curable resincomprising a polymer with polymerizable unsaturated acrylic group and anorganic solvent-soluble styrene containing an acrylic thermoplasticresin that does not need a photoinitiator.

[0009] WO 89/05827 teaches photopolymerizable adhesive compositionscomprising a copolymer of methacrylate monomer and/or methyl acrylateand a photopolymerizable monomer. These photocurable compositions,however, cannot be sufficiently cross-linked by practical irradiationenergy sources.

[0010] U.S. Pat. No. 5,446,073 and Polymer Preprints, Vol. 37, N 0.2,pp. 348-49, 1996 disclose a photopolymerizing method in which maleimidetype materials are mixed with vinyl ethers and acrylates to produce atough film. The polymerization mechanism involves a charge-transfercomplex, which is formed by an electron acceptor and an electron donor.However, many of the maleimides are solid and are hardly dissolved inacrylates.

[0011]Polymer Letters, Vol. 6, pp. 883-88,1968 reports that maleimidederivatives can be polymerized in the absence of photoinitiators underirradiation by ultraviolet light. Japanese Patent ApplicationsJP-A-61-250064, JP-A-62-64813, and JP-A-62-79243 teach energy curablecompositions comprising maleimide derivatives such as alkylmaleimidesand arylmaleimides. However, these maleimide derivatives show lowphotoinitiator properties, therefore making it necessary to usesubstantial amounts of photoinitiator in the maleimide compositions.

[0012] U.S. Pat. No. 3,920,618 and Japanese Patent applicationsJP-A-50-123138 and JP-A51-47940 disclose photopolymerizable polymershaving an α-aryl substituted maleimide group at a side chain. It is wellknown that these pendant type maleimides can be crosslinkable byultraviolet irradiation (i.e. 2+2 photocycloaddition reaction). U.S.Pat. No. 4,079,041 and Europe Patent 21019 teach polymers having sidechain type maleimide groups with alkyl substituents. However, thesependant type maleimides cannot be used to form linear polymers byphotopolymerization. Therefore they are most commonly used to preparenegative printing plates. In addition, the photocross-linkingdimerization reaction takes a rather long time (several tens seconds toseveral minutes) even with an excess amount of irradiation energy.

[0013]Polymer Materials Science and Engineering, Vol. 72, pp. 470-72,1995 and Proceedings of RadT ch Europe 95, pp. 34-56, 2995 disclosephotocurable compositions comprising maleimide derivatives as electronacceptors and vinyl ethers as electron donors. The photopolymerizablecompositions 1,4-bis(vinyloxymethyl)cyclohexane andN-cyclohexylamalemide or 4-hydroxybutyl vinyl ether and N-(hydroxyalkyl)maleimide, illustrated in these documents are polymerized upon ultraviolet irradiation in the absence of a photoinitiator. However,hardening of the coated films does not occur; i.e. the coated filmsmaintain liquid states after ultraviolet irradiation.

[0014] WO 98/07759 describes energy curable compositions whereinwater-soluble maleimides are copolymerized with acrylates in the absenceof water to produce a cured film.

[0015] The polymerizing methods described above share numerous problems,which can be summarized as the need for high irradiation intensity tocure sufficiently; the maleimide derivatives being solid at ambienttemperature which does not suggest whether they are or can behomo-polymerized upon irradiation in the absence of a photoinitiator;difficulty in obtaining cured coating with practical properties andgiven the wide range of curable composition disclosed; the need forhigher irradiation energy than practical for cross-linking(photodimerization). However, none of these references describe activeenergy curable compositions containing water or energy curablecompositions that are water compatible.

[0016] It is an object of the present invention to provide active watercompatible energy curable compositions which do not containphotoinitiator, cause unpleasant odors upon curing or cause yellowing,or exude materials from the cured film upon contact with water orsolvent. Another object of the present invention is to provide an activewater compatible energy curable composition which be photopolymerized byan energy source of practical intensity and energy value and results incoatings that exhibit cure rates, gloss, hardness and solvent resistancevalues comparable to those of conventional energy cure systems employingphotoinitiators.

SUMMARY OF THE INVENTION

[0017] The present invention is an active water curable energy curablecomposition comprising a water compatible compound, water and amaleimide derivative represented by the Formula (1):

[0018] wherein n and m each independently represent an integer of 1 to5, and the sum of m and n is 6 or smaller;

[0019] R₁₁ and R₁₂ each independently represent a linking group selectedfrom the group consisting of a straight or branched chain alkylenegroup, an alicyclic group, an arylalkylene group, and acycloalkylalkyene group. The arylalkylene group and the cycloalkylalkylene group may have an aryl or cycloalkyl group as a main chain or abranched chain, respectively;

[0020] G₁ and G₂ each independently represent ester linkage represent by

[0021] —COO— or —OCO— and;

[0022] R₂ represents a linking chain having an average molecular weightof 100 to 100,000 selected from the group consisting of (poly)ether and(poly) ester linking chains, in which at least one group consists of agroup or groups selected from a straight or branched chain alkylenegroup, an alkylene group having a hydroxyl group, an alicyclic group, anaryl group, and an arylalkylene group; and connected via at least onelinkage selected from the group consisting of an ether and esterlinkage.

DETAILED DESCRIPTION OF THE INVENTION

[0023] The active water curable energy curable compositions of thepresent invention contain a maleimide derivative of Formula 1 mentionedabove. As for variables R₁₁ and R₁₂ of Formula 1, examples R₁₁ and R₁₂suitable for use in the present invention include straight alkylenegroups such as methylene group, ethylene group, trimethylene group,tetramethylene group, pentamethylene group, hexamethylene group,heptamethylene group, octamethylene group, nonamethylene group,decamethylene group, undecamethylene group, dodecametheylne group, andthe like; alkylene groups having a branched alkyl group such as1-methylethylene group, 1-methyl-trimethylene group,2-methyl-trimethylene group, 1-methyl-tetramethylene group,2-methyl-tetramethylene group, 1-methyl-pentamethylene group,2-methyl-pentamethylene group, 3-methyl-pentamethylene group, neopentylgroup, and the like; alicyclic groups such as cyclopentylene group,cyclohexylene group and the like; arylalkylene groups having an arylgroup at a main chain or a side chain such as benzylene group,2,2-diphenyl-trimethylene group, 1-phenyl-ethylene group,1-phehyl-tetraethylene group, 2-phenyl-tetraethylene group, and thelike; cycloalkyl-alkylene group having an alicyclic group at a mainchain or a side chain such as cyclohexyl-methylene group,1-cyclohexyl-ethylene group, 1-cyclohexyl-tetraethylene group,2-cyclohexyl-tetraethylene group, and the like. However, there are noparticular limitations placed on these groups. When the averagemolecular weight of R₂, as a (poly)ether or (poly)ester linking chain isless than 100, curing properties of the maleimide thereof are worse.Even if the compositions are cured, the [gel fraction] of the energycured composition tends to be lower.

[0024] The gel fraction is the percentage of material remaining after acured film has been reflux d, for example, in methyl ethyl ketone for 3hours at 80° C., then dried at 100° C. for one hour. A cured maleimidederivative or composition, which has a 99.8% gel fraction, indicatesthat only 0.2% of the matrix was solubilized by the above refluxconditions. (i.e. a high degree of conversion).

[0025] The percentage conversion is defined as the ration of functionalgroups to a crosslinked matrix monitored by the disappearance of and IRabsorption band during the course of 20 irradiation. This real time IRmeasurement allows one to quantify percent conversion and providesinsight into the reactivity the composition during irradiation.

BRIEF OF DESCRIPTION OF THE DRAWINGS

[0026]FIGS. 1 and 2 show a plot of the percent conversion of maleimideto polymerized maleimide material over time as measured by real timeinfra red analysis.

[0027] As mentioned above, as the molecular weight of R₂ decreases, thecuring properties of the maleimide became worse. FIG. 1 shows a plot ofreal time IR data for a bismaleimide derivative (structure shown) whereR₂ is polytetramethyelene glycol. As the molecular weight of the repeatunit (n) decreases (i.e. 4000 (curve 1); 3000 (curve 2); 1000 (curve 3);650 (curve 4); and 250 (curve 5)) the conversion rate becomes lower.However, where the molecular weight of R₂ (curve 6) is less than 100,the real time IR data shows the rate of conversion to be sluggish. Thissupports employing maleimide derivatives wherein R₂ (i.e. thepoly(ether), poly(ester) linking chain) is greater than 100, since alower values yield poorer conversion rates.

[0028]FIG. 2 shows a plot of real time IR data for a bismaleimidederivative (structure shown) where R₂ is polyethylene glycol. As themolecular weight of the repeat unit (n) decreases (i.e. 1000 (curve 1);600 (curve 2); 400 (curve 3); 300 (curve 4)) the conversion ratesbecomes lower. However, where the molecular weight of R₂ (curves 5 and6) is less than 100, the real time IR data shows the rate of conversionto be sluggish.

[0029] Therefore, the results from FIGS. 1 and 2 suggest that theaverage molecular weight of R₂ be more than 100. On the other hand, whenthe average molecular weight of R₂ is more than 100,000, such as in thecase of a polyol or a polyester, the raw material for the linking chainsis solid in nature and shows poor solubility in common solvents atambient temperature. Once obtained, these maleimide derivatives arevirtually insoluble in common solvents, therefore, making it difficultto obtain a film and cure it. Even if a cured coating film is obtained,the surfaces of the coating shows unevenness. Therefore, it is notsuitable that the average molecular weight of R₂ be more than 100,000.R₂ may also be a linkage comprising an oligomer or a polymer containingthe above described (poly)ether and (poly)ester groups as repeatingunite. Examples of R₂ suitable for use in the present invention include(poly)ether or a (poly)ester linking chains having an average molecularweight in a range of 100 to 100,000.

[0030] Linking chains represented by R₂ include: a (poly)ether (poly)olresidue group; a (poly)ester (poly)ol residue group; a (poly)carboxylate{(poly)ether (poly)ol} ester having a polycarboxylic acid residue groupat a terminal end; a (poly)carboxylic acid residue group at a terminalend; a (poly)carboxylate {(poly)ester (poly) ol} ester having apolycarboxylic acid residue group at a terminal end; and (poly) epoxideforming the linking chains.

[0031] Linking chains represented by a (poly)ether (poly)ol residuegroup have an average molecular weight of 100 to 100,000, and comprisinga part in which at least one group selected from the group consisting ofa straight or branched chain C₂-C₂₄ alkylene group; a C₃-C₂₄ alicyclicgroup; and a C₆-C₂₄ aryl group, connected with an ether linking chain ora repeating unit thereof. Examples (poly)ether (poly)ol constructinglinking chain include polyalkylene glycols such as polyethylene glycol,polypropylene glycol, polybutylene glycol, polytetramethylene glycol,and the like; modified alkylene glycols in which ethylene glycol,propanediol, propylene glycol, tetramethylene glycol, pentamethyleneglycol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane,pentraeythritol, diglycerin ditrimethylolpropane, dipentaerythritol andthe like, are modified by ethylene oxides, propylene oxides, butylenesoxides and tetrahydrofuran. Among these (poly)ether (poly)ols, modifiedalkylene glycols are preferable. In addition, examples of (poly)ether(poly)ol constructing the above linking chain include hydrocarbonpolyols such as a copolymer of ethylene oxide and propylene oxide, acopolymer of propeylene glycol and tetrahydrofuran, a copolymer ofethylene glycol and tetrahydrofuran, polyisoprene glycol, hydrogenatedpolisoprene glycol, polybutadiene glycol, hydrogenated polybutadieneglycol, and the like; polyhydric alcohol compounds such aspolytetramethylene hexaglycerin ether (modified hexaglycerin bytetrahydrofuran), and the like. However, there are no particularlimitations placed on these (poly)ether (poly)ols.

[0032] Linking chains represented by a (poly)ester (poly)ol residuegroup have an average molecular weight of 100 to 100,000, and comprisinga part in which at least one group selected from the group consisting ofa straight or branched chain C₂-C₂₄ alkylene group; a C₃-C₂₄ alicyclicgroup; and C₆-C₂₄ aryl group; connected with an ester linking chain or arepeating unit thereof. Examples of (poly)ester (poly)ol constructingthe linking chain include (poly)alkylene glycols such as polyethyleneglycol, polypropylene glycol, polybutylene glycol, polytetramethyleneglycol, ethylene glycol, propane diol, propylene glycol, tetramethyleneglycol, pentamethylene glycol, hexane diol, neopentyl glycol, glycerin,trimethylolpropane, pentaerythrithol, diglycerin, ditrimethylolpropane,dipentaerythritol, diglyercin, ditrimethylolopropane, pentaerythritol,diglyercin, ditrimethylolopropane, dipentaerythirtol, and the like whichare modified by ε-caprolactone, γ-butrolactone, δ-valerolactone, andmethylvalerolactone; aliphatic polyester polyols which are synthesizedby esterification of aliphatic dicarboxylic acids such as adipic acid,dimeric acid, and the like with polyols such as neopentyl glycol,methylpentanediol, and the like; aromatic polyester polyols which aresynthesized by esterification of aromatic dicarboxylic acids such asterephthalic acid, and the like with polyols such as neopentyl glycol,and the like; ester compounds obtained by esterification of polyhydricalcohols such as polycarbonate polyol, acryl polyol,polytetramethylenehexaglyceryl ether (modified hexglycerin bytetrahydrofuran), and the like, with dicarboxylic acids such as fumaricacid, phthalic acid, isophthalic acid, itaconic acid, adipic acid,sebacic acid, maleic acid, and the like; compounds having polyol groupsuch as monoglyceride obtained by transesterification of polyhydricalcohols such as glycerin with animal and plant fatty acid esters; andthe like. However, there are no particular limitations placed on these(poly)ester (poly)ols. Linking chains represented by a (poly)carboxylate{(poly)ether (poly)ol} ester having a polycarboxylic acid residue groupat a terminal end, obtained by esterification of (poly)ether (poly)olwith C₂-C₆ carboxylic acid (the term of “C₂-C₆ carboxylic” isabbreviated as a polycarboxylic acid hereinafter), which have an averagemolecular weight of 100 to 100,000, and comprising a part in which atleast one group selected from the group consisting of a straight orbranched chain C₂-C₂₄ alkylene group; a C₃-C₂₄ alicyclic group; and aC₆-C₂₄ aryl group; connected with an ether linking chin or a repeatingunit comprising the parts. Examples of (poly) carboxylate {(poly)ester(poly)ol} ester having polycarboxylate acid at a terminal, which formsthe linking chain include (poly)carboxylate {(poly)ether (poly)ol}esters having polycarboxylic acid at a terminal end which are obtainedby esterification of polycarboxylic acids such as succinic acid, adipicacid, phthalic acid, hexhydrophthalic acid, tetrahydrophthalic acid,fumaric acid, isophthalic acid, itaconic acid, sebacic acid, maleicacid, trimellitic acid, pyomellitic acid, benezenepentacarboxylic acid,benzenehexacarboxylic acid, citric acid, tetrahydrofurantetracarboxylicacid, cyclohexanetricarboxlic acid, and the like with (poly)ether(poly)ols disclosed in the above, and the like. However, there are noparticular limitations placed on these esters.

[0033] Linking chains represented by a (poly)carboxylate{(poly)ester(poly)ol} ester having a polycarboxylic acid residue at the terminal endobtained by esterification of (poly)ester (poly)ol and polycarboxylicacid which have an average molecular weight of 100 to 100,000, andcomprising a part in which at least one group selected from the groupconsisting of a straight or branched chain C₂-C₂₄ alkylene group; aC₃-C₂₄ alicyclic group; and a C₆-C₂₄ aryl group; connected with an etherand an ester linking chains, or a repeating unit comprising the parts.Examples of (poly)carboxylate {(poly)ester (poly)ol} ester havingpolycarboxylic acid at a terminal, which forms the linking chain include(poly)carboxylate {(poly)ester (poly)ol} ester having polycarboxylicacid at a terminal end which is obtained by esterification ofpolycarboxylic acids such as succinic acid, adipic acid, phthalic acid,hexahydrophthalic acid, tetrahydrophthalic acid, fumaric acid,isophthalic acid, itaconic acid, sebacic acid, maleic acid, trimelliticacid, pyromellitic acid, benezenepentacarboxylic acid,benzenehexacarbonoxylic acid, citric acid,tetrahydrofurantetracarboxylic acid, cyclohexanetricarboxylic acid, andthe like with (poly)ester (poly)ols disclosed in the above, and thelike. However there are no particular limitations placed on theseesters.

[0034] Linking chains obtained by ring-open reaction of polyespoxideshaving an average molecular weight of 100 to 100,000, and comprising apart in which at least one group selected from the group consisting of astraight or branched chain C₂-C₂₄ alkylene group; a C₁-C₁₄ alicyclicgroup; and C₁-C₂₄ aryl group; connected with an ether linking chain, ora repeating unit comprising the parts, and the like. However, there areno particular limitations placed on these linking chains. Examples of(poly)epoxide forming the linking chain include epichlorohydrin-modifiedbisphenol type epoxy resin synthesized by the reaction of (methyl)epicholorohydrin with bisphenol A, bisphenol F, modified ethylene oxidethereof, modified propylene oxide thereof; epichlorohydrin-modifiedhydrogenated bisphenol type epoxy resin synthesized by the reaction of(methyl) epichlorohydrin with hydrogenated bisphenol A and hydrogenatedbisphenol F, and by the reaction of ethylene oxide-modified or propyleneoxide modified hydrogenated bisphenol A and bisphenol F; epoxy novolakresin; compounds obtained from the reaction of phenol, bisphenol, andthe like with (methyl) epichlorohydrin; aromatic epoxy resin such asglycidyl ester of terephthalic acid, isophthalic acid, pyromelliticacid, and the like; polyglycidyl ethers synthesized from glycols such as(poly)ethylene glycol, (poly)propylene glycol, (poly)butylene glycol,(poly)tetramethylene glycol, neopentyl glycol, and from alkyleneoxide-modified glycols thereof; polyglycidyl ethers synthesized fromaliphatic polyhydric alcohols such as trimethylol propane, trimethylolethane, glycerin, diglycerin, erythritol, pentaerythritol, sorbitol,1,4-butane diol, 1,6-hexane diol, and the like, and from alkyleneoxide-modified aliphatic polyhydric alcohols thereof; glycidyl esterssynthesized from adipic acid, sebacic acid, maleic acid, itaconic acid,and the like; glycidyl ether of polyester polyol synthesized frompolyhydric alcohol with polycarboxylic acid; copolymers such as glycidyl(meth)acrylate and methylglycidyl(meth)acrylate; aliphatic epoxy resinsuch as glycidyl ester of higher fatty acid, epoxidized linseed oil,epoxidized soybean oil, epoxidized castor oil, epoxidized polybutadiene;and the like. However, there are no particular limitations paced onthese (poly) epoxides.

[0035] Among the linking chains R₂ represents, preferred are (poly)etherand (poly)ester linking chains having an average molecular weight of 100to 100,000 and comprising a repeating unit containing a C₂-C₂₄ straightchain or branched alkylene, a C₂-C₂₄ alkylene group having a hydroxylgroup, and/or a C₆-C₂₄ aryl group.

[0036] The maleimide derivatives represented by Formula (1) used for anactive energy curable composition of the present invention can besynthesized by well known techniques from the reaction of, for example,a maleimide compound having a carboxyl group with a compound reactablewith the carboxyl groups or from the reaction of maleimide compoundhaving a hydroxyl group with a compound having a carboxyl group.

[0037] A maleimide compound having a carboxyl group can be synthesizedby well known techniques from the reaction of maleic anhydride with aprimary amino carboxylic acid, represented by the following reactionformula. (for example, see D. H. Rich, et al., Journal of MedicalChemistry, Vol. 18, pp. 1004-10, 1975).

[0038] Examples of a primary amino carboxylic acid suitable for use insuch synthesis includes asparagine, alanine, β-alanine, arginine,isoleucine, glycine, glutamine, tryptophan, threonine, valine,phenylalanine, homophenylalanine, α-methyl-phenylalanine, lysine,leucine, cycloleucine, 3-aminoproprionic acid, α-aminobuytric acid,4-aminobutyric acid, aminovalieric acid, 6-aminocaproic acid,7-aminoheptanoic acid, 2-aminocarprylic acid, 3-aminocaprylic acid,6-aminocaprylic acid, 8-aminocaprylic acid, 2-aminonoanoic acid,4-aminonoanoic acid, 9-aminonoanoic acid, 2-aminocapric acid,9-aminocapric acid, 10-aminocapric acid, 2-aminocapric acid,9-aminocapric acid, 10-aminocapric acid, 2-aminoundecanoic acid,10-aminoundecanoic acid, 11-aminoundecanoice acid, 2-aminolauric acid,11-aminolauric acid, 12-aminolauric acid, 2-aminotridecanoic acid,13-aminotridecanoic acid, 2-amino myristic acid, 14-amino myristic acid,2-aminopentadecanoic acid, 15-aminopentadecanoic acid, 2-aminopalmiticacid, 16 aminotpalmitic acid, 2-aminoheptadecanonic acid,17-aminoheptadecanoic acid, 2-aminostearic acid, 18-aminostearic acid,2-aminoeicosancoic acid, 20-aminoesicosanoic acid,aminocyclohexanecarboxylic acid, aminomethylcyclhexane-carboxylic acid,2-amino-3propionic acid, 3-amino-3phenylpropionic acid, and the like.However, there are no particular limitations placed on these primaryamino carboxylic acids as virtually any primary amino carboxylic acidcan be used. In addition, pyrrolidone, lactams such as δ-valerolactam,ε-carpolactam, and the like can also be used.

[0039] Examples of compounds reactive with the carboxyl groups includepolyols or polyespoxides having 2 to 6 functional groups and an averagemolecular weight of 100 to 100,000 comprising a part or a repeating unitin which at least one linking group selected from the group consistingof a straight chain alkylene group, a branched alkylene group, andalicyclic group and an aryl group is linked with an ether bond and/or anester bond.

[0040] There are no particular limitations placed on the reactionbetween maleimide compounds having a carboxyl group and polyols one ofthe compound reactive with the carboxyl groups. Moreover, maleimidederivatives represented by Formula (1) can be synthesized in awell-known manner disclosed in Organic Synthesis Collective Volume (C.E. Rehberg, et al., Vol. 3, pp. 46, 1955). It is preferable, however,that the reaction be carried out under ambient or reduced pressure, anda temperature ranging from room temperature to 150° C., whiledehydrating and using a catalyst. Examples of the catalyst include acidcatalysts such as sulfuric acid, phosphoric acid, methanesulfonic acid,benzenesulfonic acid, p-toulensesulfonic acid, strong acidiccation-exchange resin and the like. The amount of catalyst used shouldbe within a range of 0.01 to 10 wt. % based on the total weight of rawmaterials. Moreover, an azeotropic organic solvent with water is alsoused as a solvent in the reaction. Examples of the azeotropic organicsolvent with water include toluene, benzene, butyl acetate, ethylacetate, diisopropyl ether, dibutyl ether, and the like.

[0041] There are no particular limitations placed on the reaction of themaleimide compounds having a carboxyl group with polyepoxides, which areone of the reactive compounds with the carboxyl groups. In addition,maleimide derivatives represented by Formula (1) can be synthesized in awell-known manner disclosed in Japanese Patent ApplicationJP-A-4-228529. It is preferable, however, that the reaction be carriedout at a temperature in a range of room temperature to 150° C., using acatalyst. Examples of the catalyst include imidazoles such as2-methylmidazole and the like; quaternary ammonium salts such astetramethyl ammonium chloride, trimethylbenzyl ammonium chloride,tetramethyl ammonium bromide and the like; amines such astrimethylamine, triethylamine, benzylmethylamine, tributylamine, and thelike; phosphines such as triphenylphoshine, tricyclohexylphosphine, andthe like; laurates such as dibutylin laureate, and the like; basicalkali metal salts such as potassium acetate, potassium tertiaryphosphate, sodium acrylate, sodium methacrylate and the like; alkalialcoholates such as sodium methylate, potassium ethylate, and the like;anion exchange resins; and the like. The amount of catalyst should bewithin a range of 10 to 10,000 ppm based on the total weight of rawmaterials.

[0042] Moreover, an organic solvent, which does not comprise a reactivehydrogen, may also be used as a solvent in the reaction. Examples of anorganic solvent which does not comprise a reactive hydrogen includearomatic hydrocarbons such as toluene, ethylbenzene, tetralin, cumene,xylene and the like; ketone, cyclohexanone, and the like; esters such asformate, methyl acetate, ethyl acetate, n-butyl acetate, and the like.

[0043] Examples of polyols used as a compound reactive with the carboxylgroups include, for example, polyalkylene glycols such as polyethyleneglycol, polypropylene glycol, polybutylene glycol, polytetramethyleneglycol, and the like; modified alkylene glycols modified of alkyleneglycols such as ethylene glycol, propanediol, propylene glycol,butanediol, butylene glycol, hexanediol, neopentyl glycol, glycerin,trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane,dipentaerythritol, and the like by ethyleneoxide, propylene oxide,butyleneoxide, tetrahydrofuran, ε-caprolactone, γ-butylolactone,δ-valerolactone, and methylvalerolactone; aliphatic polyols such as acopolymer of ethylene oxide with propylene oxide, a copolymer ofpropylene glycol with tetrahydrofuran, a copolymer f ethylene glycolwith tetrahydrofuran, polyisoperene glycol, hydrogenated polyisopreneglycol, polybutadiene glycol, hydrogenated polybutadiene glycol, and thelike; aliphatic polyester polyols which are the esterification reactionproducts of aliphatic dicarboxylic acids such as adipic acid and dimericacid with polyols such as neopentyl glycol and methylpentanediol, andthe like; aromatic polyester polyols which are the esterificationreaction products of aromatic dicarboxlic acids such as terephthalatewith polyols such as neopentyl glycols; polycarbonate polyols;acrylpolyols; polyhydric alcohols such as polytetramethylenehexaglycerinether (tetrahydrofuran-modified hexaglycerin); compounds containingmonohydroxyl group with polyhydroxy groups, and having an ether group atterminal ends of the polyhydric alcohols described above; compoundscontaining polyhydroxyl groups obtained by the esterification reactionof the above polyhydric alcohols with dicarboxylic acids such as fumaricacid, phthalic acid, isophthalic acid, itaconic acid, adipic acid,sebacic acid, maleic acid, and the like; compounds containingpolyhydroxyl groups obtained by the transesterification reaction ofcompounds containing polyhydroxyl groups such as glycerin with ester offatty acids of animals and plants. Any polyols maybe used if theycontain 2 to 6 hydroxyl groups in the molecule.

[0044] Examples of polyepoxides used as the compound reactive with thecarboxyl groups include, for example, bisphenol type epoxy resinsmodified by epichlorohydrin, which are synthesized by(methyl)epichlorohydrin with bisphenol A, and bisphenol F, and theirmodified compounds by ethyleneoxide, propyleneoxide, and the like;hydrogenated bisphenol type epoxy resins and epoxy Novolak® resins(Novolak is a Registered Trademark of Shell Company, Houston, Tex.)modified by epichlorhydrin which are synthesized by (methyl)epichlorhydrin which are synthesized by (methyl) epichlorohydrin withhydrogenated bisphenol A, hydrogenated bisphenol F, and their modifiedcompounds by ethyleneoxide propyleneoxides, and the like; reactionproducts of (methyl) epichlorohydrin with phenol and biphenol; aromaticepoxy resins such as glycidl esters of terephthalic acid, isophthalicacid, and pyrrolitic acid; polyglycidyl ethers of glycols such as(poly)ethylene glycol, (poly)propylene glycol, (poly)butylene glycol,(poly)tetramethylene glycol, and their alkyleneoxide-modified products;glycidyl ethers modified of aliphatic polyhydric alcohols such astrimethlolpropane, trimethylolethane, glycerin, diglyercin, erythritol,pentaerythritol, sorbitol, 1 4-butanediol, 1,6-hexanediol, and theiralkyleneoxide-modified compounds; glycidyl esters of carboxylic acidssuch as adipic acid, sebacic acid, maleic acid, and itaconic acid;glycidyl ethers of polyester polyols prepared by polyhydric alcohols andpolycarboxylic acids; copolymers of glycidyl(meth)acrylate andmethylglycidyl(meth)acrylate; aliphatic epoxy resins such as glycidlesters of higher fatty acids, epoxidized linseed oil, epoxidized soybeanoil, epoxidized castor oil, and epoxidized polybutadiene.

[0045] The maleimide derivatives represented by Formula (1) used for anactive energy curable composition of the present invention can also besynthesized by the reaction of a maleimide compound having a hydroxylgroup with a compound having a carboxyl group.

[0046] Moreover, a maleimide compound having a hydroxyl group can besynthesized by maleimide and formaldehyde, represented by the reaction:

[0047] or by a well-known technique using maleic anhydride and a primaryamino alcohol represented by the reaction:

[0048] (for detailed synthesis example, see U.S. Pat. No. 2,526,517 andJapanese Patent Application JP-A-2-268155).

[0049] Examples of a primary amino alcohol include 2-aminoethanol,1-amino-2-propanol, 3-amino-1-propanol, 2-amino-2-methyl-1-propanol,2-amino-3-phenyl-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol,2-amino-3-methyl-1-butanol, 2-amino-4-methylthio-1butanol,2-amino-1-pentanol, 5-amino-1-pentanol, (1-aminocyclopentane)methanol,6-amino-1-hexanol, 2-amino-1-hexanol, 7-amino-1-heptanol,2-(2-aminoethoxy) ethanol, N-(2-aminoethyl)ethanol amine,4-amino-1-piperazne ethanol, 2-amino-1-phenylethanol,2-amino-3-phenyl-1-propanol, 1-aminomethyl-1-cyclohexanol,aminotrimethylcyclohexanol, and the like. However, there are noparticular limitations placed on these primary amino alcohols. Anyprimary amino alcohol can be used.

[0050] Examples of compounds reactive with the hydroxyl groups includepolycarboxylic acid having ether bonds and/or ester bonds in onemolecule, and an average molecular weight of 100 to 100,000, and thecomprising a part or a repeating unit in which at least one linkinggroup selected from the group consisting of a straight chain alkylenegroup, a branched alkylene group, an alicyclic group, and an aryl group;linked with an ether bond and/or an ester bond.

[0051] There are no particular limitations placed on the reactionbetween the maleimide compounds having a hydroxyl group and thecompounds having a carboxyl group. In addition, maleimide derivativesrepresented by Formula (1) can be synthesized in a well-known mannerdisclosed in Organic Synthesis Collective Volume (C. E. Rehberg, et al.,Vol. 3, pp. 46, 1955). It is preferable, however, that the reaction becarried out under ambient or reduced pressure, at a temperature rangingfrom room temperature to 150° C. while dehydrating and using a catalyst.Examples of the catalyst include acid catalysts such as sulfuric acid,phosphoric acid, methanesufonic acid, benzenesulfonic acid,p-toluenesulfonic acid, strong acid cation-exchange resin, and the like.The amount of catalyst should be within a range of 0.01 to 10 wt. %based on the total weight of raw materials.

[0052] In this case, as the solvent for the reaction, it is possible touse organic solvents, which are azeotropic with water. Examples of suchorganic solvents are toluene, benzene, butyl acetate, ethyl acetate,diisopropryl ether, and dibutyl ether, and the like.

[0053] In any cases of the above reactions, it is preferable to use aradical polymerization inhibitor in order to suppress the radicalpolymerization of maleimide groups. The radical polymerizationinhibitors include, for example, phenol, derivatives such ashydroquinone, tert-butylhydroquinone, methoquinone,2,4-dimethyl-6-tert-butylphenol, catecol, tert-butylcatecol, and thelike; amines such as phenothiazine, p-phenylenediamine, diphenylamineand the like; copper complexes such as copper-dimethyldithiocarbamate,copper-diethyldithiocarbamate, copper-dibutyldithiocarbamate, and thelike. These inhibitors may be used alone or in combinations of two ormore. It is preferable to select an amount of the inhibitors within arange of 10 to 10,000 ppm against total weight of raw materials.

[0054] Examples of polycarboxylic acids as the compounds, having etherbonds and ester bonds, include, for example, but are not limited to,polycarboxylic acids obtained by esterification or dicarboxylic acidssuch as fumaric acid, phthalic acid, isophthalic acid, itaconic acid,adipic acid, sebacic acid, maleic acid, succinic acid, hexahydrophthalicacid, tetrahydrophthalic acid, pyromellitic acid, and dicarboxylic aciddescribed above with polyols described above, and represented byformula:

HOOC—X′—COO—Y′OOC—X′—COOH)_(n)

[0055] wherein x′represents residual diarboxyl groups, Y′ representresidual polyol groups, and n is an integer from 1 to 5.

[0056] The maleimide derivatives represented by Formula (1) and used forthe active energy curable composition of the present invention areobtained by aforementioned preparatory methods, but are not limited to,the methods described herein.

[0057] It is possible to add a compound, which copolymerizable with themaleimide groups to be used together in the active energy curablecomposition containing maleimide derivatives according to the presentinvention. Practical examples of the compounds, which arecopolymerizable with the maleimide groups, are, for example, compoundshaving various unsaturated double bonds. Such compounds may include, forexample, maleimide derivatives which are not represented by the aboveFormula (1), (meth)acryoyl derivatives, (meth)acrylamide derivatives,vinyl ester derivatives, vinyl carboxylate derivatives, styrenederivatives, and unsaturated polyesters.

[0058] Examples of maleimide derivatives which are not represented byFormula (1) include, for example, but are not limited to:

[0059] monofunctional aliphatic maleimides such as N-methylmaleimide,N-ethylmalemide, N-propylinaleimide, N-nbutylmaleimide,N-tert-butylmaleimide, N-pentylmaleimide, N-hexylmaleimide,N-laurylmaleimide, 2-maleimideethyl-ethylcarbonate,2-maleimideethyl-isopropyl-carbonate, and N-ethyl-(2-malemideethyl)carbamate; monofunctional alicyclic maleimides such asN-cyclohexylmaleimide: aromatic monofunctional maleimides such asN-phenylmaleimide, N-2methylphenylmaleimide, N-2-ethylphenylmaleidmide,N-(2,6-diethylphenyl) maleimide, N-2-chlorophenylmaleimide, andN44-hydroxyphenyl) maleimide;

[0060] aliphatic bismaleimides such as N,N′methylenebismaleimide,N,N′-ethylenebismaleimide, N,N′trimethylenebismaleimide,N,N′-hexamethylenebismaleimide, N,N′-dodecamethylenebismaleimide,polypropylene glycol-bis(3-maleimidepropyl)ether, tetraethyleneglycol-bis (3-maleimidepropyl)ether, and bis(2-maleimideethyl)carbonate;

[0061] alicyclic bismaleimides such as 1,4-dimaleimide-cyclohexane andisophoronebisurethanebis(N-ethylmalemide); aromatic bismaleimides suchas N,N′-(4,4″-diphenyl-methane)bismaleimide,N,N′-(4,4′-diphenyloxy)bismaleimide, N, N′-p-phenylenebismaleimide,N,N′-m-phenylenebismaleimide, N,N′-2,4-tolylenebismaleimide,N,N′-2,6-tolylenebismaleimideN,N′-[4,4′-bis(3,5-dimethylphenyl)methane]bismaleimide,N,N′-[4,4′-bis(3,5-diethylphenyl)methane]bismaleimide;

[0062] (poly)urethane (poly)maleimide derivatives obtained byurethanation reactions of hydroxymaleimides with various(poly)isocyanantes, such as a maleimide derivative obtained by aurethanation reaction of hydroxyethylmaleimide with triisocynateproduced by a reaction between 3 mole of isophoronediisocyanante and 1mole of propyleneoxide-modifified-glycerin;

[0063] a maleimide derivative obtained by a urethanation reaction ofhydroxymethylmaleimide with diisocyanate produced by a reaction between2 moles of 2,4-toluenediisocyanante and 1 mole ofpolytetramethyleneglycol; and

[0064] compounds having acryloyoxyl groups or methacryloyoxy groups canbe classified into, but are not limited to, groups of (poly)ester(meth)acrylate; urethane (meth)acrylate; epoxy(meth)acrylate;(poly)ether (meth)acrylate; alkyl(meth)acrylate or alkylene(meth)acrylate; (meth) acrylate having an aromatic ring and;(meth)acrylate having an alicyclic group.

[0065] Names in the above classification are used as the general termsfor respective compounds, which can be used together in the activeenergy curable composition of the present invention. The (poly)ester(meth)acrylate generally designates (meth)acrylates having at least oneester bond in the main chain; urethane (meth)acrylate generallydesignates (meth)acrylates having at least one urethane bond in the mainchain; the epoxy acrylate generally designates (meth)acrylates obtainedby a reaction between (meth)acrylic acid and epoxide with one and morethan one functional group the (poly)ether (meth)acrylate generallydesignate (meth)acrylates having at least one ether bond in the mainchain; the alkyl(meth)acrylates or alkylene (meth)acrylate generallydesignates (meth)acrylates comprising the main chain formed by a linearalkyl, a branched alkyl, a linear alkylene, or a branched alkylene, andside chains or terminal ends having halogen atoms and/or hydroxylgroups; (meth)acrylate having an aromatic ring generally designates(meth)acrylate having an aromatic ring at the main chain or the sidechain; (meth)acrylate having an alicyclic group generally designates(meth)acrylates having, in the main chain or the side chain, alicyclicgroups which may include oxygen atoms or nitrogen atoms as thestructural unit.

[0066] Examples of the (poly)ester (meth)acrylates which can be usedtogether in the active energy curable composition of the presentinvention include, for example, but are not limited to, monofunctional(poly)ester (meth)acrylates such as alicyclic-modifiedneopentylglycol(meth)acrylate, caprolactone-modified2-hydroxyethyl(meth)acrylate, ethyleneoxide-and/orpropyleneoxide-modified phthalate (meth)acrylate, ethyleneoxide-modifiedsuccinate (meth)acrylate, caprolactone-modifiedtetrahydrafurfuryl(meth)acrylate;pivalate-esterneopentylglycoldi(meth)acrylate, caprolactone-modifiedhydroxypivalateesterenepentylglucoldi(meth)acrylate,epicholohydrine-modified phthalated (meth)acrylate; mono-, di ortri-(meth)acrylates of triol obtained by addition of more than 1 mole ofcyclic lactones such as ε-caprolactone, γ-butylolactone, δ-valerolactoneor methylvalerolactone to 1 mole of trimethyl lpropane or glycerin;mono-, di-tri, or tetra(meth)acrylates of triol obtained by addition ofmore than 1 mole of cyclic lactones such as ε-caprolactone,γ-butylolactone, δ-valerolactone or methylvalerolactone to 1 mole ofpentaerythritol or ditrimethylolopropane; mono- or poly(-meth)acrylatesof polyhydric alcohols such as triol, tetraol, pentaol, or hexaol,obtained by addition of more than 1 mole of cyclic lactones such asε-carpolactone, γ-butylolactone, δ-valerolactone or methylvalerolactoneto 1 mole of dipentaerythritol; (meth)acrylates of polyester polyolscomposed of diol components such as (poly)ethylene glycol,(poly)propylene glycol, (poly)tetramethylene glycol, (poly)butyleneglycol, (poly)pentanediol, (poly)methylpentanediol, and(poly)hexanediol, and polybasic acids such as maleic acid, fumaric acid,succinic acid, adipic acid, phthalic acid, hexahydrophthalic acid,tetrahydrophthalic acid, itaconic acid, citraconic acid, hettic acid,chlorendic acid, dimeric acid, alkenylsuccinic acid, sebacic acid,azelaic acid, 2,2,4-trimethyladipic acid, 1,4-cyclohexanedicarboxylicacid, terephthalic acid, 2-sodium-sulfoterephthalic acid, 2-potassiumsulfoterephthalic acid, isophthalic acid, 5-sodium sulfoisophthalicacid, 5-potassium sulfiosophtahlic acid, orthophthalic acid,4-sulfophthalic acid, 1,10-decamethylenedicarboxylic acid, muconic acid,oxalic acid, malonic acid, gultaric acid, trimellitic acid, pyromelliticacid; and polyfunctional (poly)ester (meth)acrylates composed of theabove diol components, polybasic acids, and cyclic lactone-modifiedpolyesterdiols such as ε-carpolactone, γ-butylolactone, δ-valerolactoneor methylvalerolactone.

[0067] The urethane (meth)acrylate which can be used together in theactive energy curable composition of the present invention is a generalterm representing (meth)acrylates obtained by a reaction between hydroxycompounds having at least one acryloyloxy group and isocyanantecompounds. The urethane (meth)acrylate may also be selected from waterdilutable aliphatic acrylate or aromatic urethanes.

[0068] Examples of hydroxy compounds having at least one acryloyoxygroup include, for example, 2-hydroxyethyl(meth)acrylate,2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate,3-hydroxybutyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate,cyclohexanedimethanolmono(meth)acrylate, polyethyleneglycol(meth)acrylate, polypropylene glycol(meth)acrylate,trimethylolpropanedi(meth)acrylate, trimethylolethanedi(meth)acrylate,pentaerythritoltri(meth)acrylate or an adduct of (methacrylate withglycidyl(meth)acrylate, (meth)acrylate compounds having hydroxyl groupssuch as 2-hydroxy-3-phenopropyl(meth)acrylate, and ring opening reactionproducts of the above acrylate compounds having hydroxyl group with asε-caprolactone.

[0069] Examples of isocyanate compounds include, for example, aromaticdiisocyanates such as p-phenylenediisocyanate, m-phenylenediisocyanate,p-xylenediisocyanante, m-xylenediisocyanate, 2,4-toluenediisocyanate, 2,6-toluenediisocyanate, 4,4′-diphenylmethanediisocyanate,3,3′-dimethyldiphenyl-4,4′-diisocyanate,3,3′-diethyldiphenyl-4,4′-diisocyanate, and naphthalenediisocyanate;aliphatic or alicyclic diisocyanates such as isophoronediisocyanate,hexamethylenediisocyanate, 4,4′-dicyclohexlymethanediisocayanate,hydrogenated xylenediisocyante, norborenendiisocyanate, andlysinediisocyanate, polyisocyanates such as buret products of more thanone type of isocyanates and isocyanates-trimers of the aboveisocyanates; and polyisocyanates obtained by the esterification reactionof the above isocyanate with various polyols.

[0070] Examples of polyols used to produce polyisocyanates include, forexample, (poly)alkylene glycols such as (poly)ethylene glycol,(poly)propylene glycol, (poly)butylene glycol, and (poly)tetramethyleneglycol; alkyleneglycols modified by ethyleneoxide, propyleneoxide,butyleneoxide, tetrahydrofuran, ε-caprolactone, γ-butylolactone,δ-valerolactone or methylvalerolactone, such as ethylene glycol,propanediol, propylene glycol, tetramethylene glycol, pentamethyleneglycol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane,pentaerythritol, diglycerin, ditrimethylolpropane, anddipentaerythritol; aliphatic polyols such as copolymers of ethyleneoxideand propyleneoxide, copolymers of propylene glycol and tetrahydrofuran,copolymers of ethylene glycol and tetrahydrofuran, polyisoprene glycol,hydrogenated polyisoprene glycol, polybutadiene glycol and hydrogenatedpolybutadiene glycol, aliphatic polyester polyols obtained byesterification reactions between aliphatic dicarboxylic acids such asadipic acid and dimeric acid with polyols such as neopentyl glycols andmethylpentanediol; aromatic polyester polyols obtained by esterificationreactions between aromatic dicarboxylic acids such as terephthalic acidwith polyols such as neopentyl glycol; polycarbonatepolyols;acrylpolyols; polyhydric alcohols such as polytetramethylenehexaglycerylether (hexaglycerin modified by tetrahydrofuran); mono- or polyhydriccompounds having of the above compounds having ether group at aterminal; polyhydric compounds obtained by esterification of thecompounds having polyhydroxyl groups with dicarboxylic acids such asfumaric acid, phthalic acid, isophthalic acid, itaconic acid, adipicacid, sebacic acid, and maleic acid; compounds containing polyhydroxylgroup such as monoglyceride obtained by transesterification reactions ofcompounds having polyhydroxyl groups such as glycerin with ester offatty acids of animals or plants.

[0071] Epoxy(meth)acrylates capable of being used together in the activeenergy curable composition of the present invention is a general termfor (meth)acrylate obtained by a reaction of epoxides having more thanone functional group and (meth)acrylic acids. Epoxides as the rawmaterial of epoxy(meth)acrylate includes, for example, but are notlimited to, epichlorhydrin-modified-hydrogenated bisphenol-type epoxyresin, synthesized by (methyl)epicholohydrin and compounds such ashydrogenated bisphenol A, hydrogenated bisphenol S, hydrogenatedbisphenol F, and their modified compounds with ethylene oxide orpropylene oxide; alicyclic epoxy resins such as3,4-epoxycyclohexylmethyl-3,4-epoxycyclo hexane carboxylate,bis-(3,4-epoxycyclohexyl) adipate; alicylic epoxides such as epoxy resincontaining heterocycles such as triglycidylisocyanurate,epichlorohydrin-modified bisphenyl-type epoxy resins synthesized by areaction of (methyl) epichlorohydrin and a compound such as bisphenol A,bisphenol S, bisphenol F, and their modified compounds with ethyleneoxide or propyleneoxide; phenol Novolak type epoxy resins; cresolNovolak type epoxy resins; epoxy resins of diccylopentadiene-modifiedphenol resin obtained by the reaction of dicyclopentadiene and varioustypes of phenol resins; an aromatic epoxidized compounds of2,2′6,6′-tetramethylbisphenol; aromatic epoxides such as phenylglycidylether; (poly)glycidyl ethers of glycol compounds such as (poly)ethyleneglycol, (poly)propylene glycol, (poly)butylene glycol,(poly)tetramethylene glycol, neopentyl glycol; (poly)glycidyl ether ofglycols modified with alkylene oxide; (poly)glycidyl ethers of aliphaticpolyhydric alcohols such as trimethylolpropane, trimethylolethane,glycerin, diglycerin, erythritol, pentaerythritol, sorbitol,1,4-butanediol, 1,6-hexanediol; alkylene type epoxides of (poly)glycidylether modified of aliphatic polyhydric alcohols by alkylene;glycidylester of carboxylic acids such as adipic acid, sebacic acid,maleic acid, and itaconic acid; glycidyl ethers of polyesterpolyols ofpolyhydric alcohols with polycarboxylic acids; a copolymer ofglycidyl(meth)acrylate or methglycidl(meth)acrylate; glycidylester ofhigher fatty acids; aliphatic epoxy resins such as an epoxydized linseedoil, an epoxydized castor oil, and an epoxydized polybutadiene.

[0072] (Poly)ether (meth)acrylates capable of being used together in theactive energy curable composition of the present invention include, forexample, but are not limited to, aliphatic epoxy acrylates,monofunctional (poly)ether(meth)acrylates such asbutoxyethyl(meth)acrylate, butoxytrietheylene glycol(meth)acrylate,epichlorohydrin-modified butyl(meth)acrylate,dicyclopentanyloxyethyl(meth)acrylate, 2-ethoxyethyl(meth)acrylate,ethylcarbitol(meth)acrylate, 2-methoxy(poly)ethylene glycol(meth)acrylate, methoxy(poly)propylene glycol (meth)acrylate,nonylphenoxypolyethylene glycol (meth)acrylate,nonylphenoxypolypropylene glycol (meth)acrylate, phenoxyhydroxpropyl(meth)acrylate, phenoxy(poly)ethylene glycol (meth)acrylate,polyethylene glycol mono(meth)acrylate, polypropylene glycolmono(meth)acrylate; and polyethylene glycol, polypropylene glycolmono(meth)acrylate; alkylene glycol di(meth)acrylates such aspolyethylene glycol di(meth)acrylate, polypropylene glycoldi(meth)acrylate, polybutylene glycol di(meth)acrylate,polytetramethylene glycol di(meth)acrylate; polyfunctional(meth)acrylates induced by (meth)acrylic acid with aliphatic polyolssuch as a copolymer of ethylene oxide and propylene oxide, a copolymerof propylene glycol and tetrahydrofuran, a copolymer of ethylene glycoland tetrahydrofuran, polyisoprene glycol, hydrogenated polyisopreneglycol, polybutadieneglycol, hydrogenated poybutadiene glycol,polyfunctional (meth)acrylates induced by acrylic acid with polyhydricalcohols such as polytetramethylenehexaglyceryl ether(tetrahydrofuran-modified hexaglycerin); di(meth)acrylates of diolobtained by addition of equimolar or more than 1 mole of cyclic etherssuch as ethylene oxide, propylene oxide, butylene oxide and/ortetrahydrofuran to 1 mole of neopentyl oxide; di(meth)acrylates ofalkylene-oxide modified bisphenols such as bisphenol A, bisphenol F andbisphenol S; di(meth) acrylate of alkylene oxide-modified hydrogenatedbisphenols such as hydrogenated bisphenol A, hydrogenated bisphenol F,hydrogenated bisphenol S; di(meth)acrylates of alkylene oxide-modifiedtrisphenols; di(meth)acrylates of alkylene oxide-modified hydrogenatedtrisphenols; di(meth)acrylates of alkylene oxide-modified p,p′-bisphenols; di(meth)acrylates of alkylene oxide-modified hydrogenatedbisphenols; di(meth)acrylates of alkylene oxide-modified p,p′-dihydroxybenzophenones, mono-, di- and tri-(meth)acrylates of triolsobtained by addition of equimolar or more than 1 mol of ethylene oxide,propylene oxide, butylene oxide, and/or cyclic ethers such astetrahydrofuran to 1 mole of trimethylelolpropane or glycerin; mono-,di-, tri- or tetra-(meth)acrylates obtained by addition of equimolar ormore than 1 mole to ethylene oxide, propylene oxide, butylene oxide,and/or cyclic ethers such as tetrahydrofuran to 1 mole ofpentaerylthritol, ditrimethylolpropane or highly alkoxylatedtrimethylolpropane triacrylate; monofunctional (poly)ether(meth)acrylates or polyfunctional (poly)ether(meth)acrylates ofpolyhydric alcohols such as triol, tetraol, pentaol, or hexaol of mono-or poly-(meth)acrylates obtained by addition of equimolar or more than 1mole of ethylene oxide propylene oxide, butylene oxide, and/or cyclicethers such as tetrahydrofuran to 1 mole of dipentaerythritol.

[0073] Alkyl(meth)acrylates or alkylene(meth)acrylates which can be usedtogether in the active energy curable composition of the presentinvention include, for example, but are not limited to, monofunctional(meth) acrylates such as methyl(meth)acrylate, ethyl(meth)acrylate,propyl(meth)acrylate, isopropyl(meth)acrylate, butyl(meth)acrylate,isobutyl(meth)acrylate, pentyl(meth)acrylate, isopentyl(meth)acrylate,neopentyl(meth)acrylate, hexyl(meth)acrylate, heptyl(meth)acrylate,2-ethylhexyl(meth)acrylate, octyl(meth)acrylate, isooctyl(meth)acrylate,nonyl(meth)acrylate, decyl(meth)acrylate, dodecyl(meth)acrylate,tridecyl(meth)acrylate, pentadecyl(meth)acrylate;miristyl(meth)acrylate, palmityl(meth)acrylate, stearyl(meth)acrylate,neryl(meth)acrylate, geranyl(meth)acrylate, farnecyl(meth)acrylate,hexadecyl(meth)acrylate, octadecyl methacrylate, docosyl(meth)acrylate,and trans-2-hexene(meth)acrylate; di(meth)acrylates of aliphatic diolssuch as ethylene glycol di(meth)acrylate, propylene glycoldi(meth)acrylate, 1,2-butylene glycol di(meth)acrylate, 1,3-butyleneglycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, neopentyl glycol di(meth)acrylate,2-methyl-1,8-octanediol di(meth)acrylate 1,9-nonanedioldi(meth)acrylate, and 1,10-decanediol di(meth)acrylate;mono(meth)acrylates or poly(meth)acrylates of polyhydric alcohols suchas trimethylolpropane, (hereinafter, the term “poly”) is used as thegeneral term of the polyfunctionals including di, tri, tetra, and polycompounds such as mono(meth)acrylate, di(meth)acrylate, andtri(meth)acrylate of trimetylolpropane), and mono(meth)acrylates orpoly(meth)acrylates of polyhydric alcohols such as triol, tetraol andhexaol, for example, glycerin, pentaerythritol, ditrimethylolopropane,and dipentaerythritol; (meth)acrylates having hydroxyl groups such s2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate,4-hydroxybutyl(meth)acrylate, 3-chloro-2-hydroxyethyl(meth)acrylate;(meth)acrylates having bromine atoms such as2,3-dibromopropyl(meth)acrylate, tribomophenyl(meth)acrylate, etheyleneoxide-modified tribomophenyl(meth)acrylate, ethylene oxide-modifiedtetrabromobisphenol A di(meth)acrylate; (meth)acrylates having fluorineatoms such as trifluoroethyl(meth)acrylate,pentafluoropropyl(meth)acrylate, tetrafluoropropyl(meth)acrylate,octafluoropentyl(meth)acrylate, dodecafluoroheptyl(meth)acrylate,hexadecafluorononyl(meth)acrylate, hexfluorobutyl(meth)acrylate,3-perflurobutyl-2-hydroxypropyl(meth)acrylate,3-perflurohexyl-2-hydroxypropyl(meth)acrylate,3-perfluorooctyl-2-hydroxypropyl(meth)acrylate,3-(perfluro-5-methylhexyl)-2-hydroxypropyl(meth)acxrylate3-(perfluro-7-methyloctyl)-2-hydroxypropyl(meth)acrylate, and3-(perflouro-8-methyldecyl)-2-hydroxypropyl(meth)acrylate.

[0074] (Meth)acrylates having aromatic groups which can be used togetherin the active energy curable composition of the present inventioninclude, for example, but are not limited to, monofunctional(meth)acrylates such as phenyl(meth)acrylate, benzylacrylate; anddi(meth)acrylates such as bisphenol A diacrylate, bisphenol Fdiacrylate, bisphenol S diacrylate.

[0075] (Meth)acrylates having alicyclic groups which can be usedtogether in the active energy curable composition of the presentinvention include, for example, but are not limited to, monofunctional(meth)acrylates having alicyclic structures such ascyclohexyl(meth)acrylate, cyclopentyl(meth)acrylate,cycloheptyl(meth)acrylate, bicycloheptyl(meth)acrylate,isobornyl(meth)acrylate, bicyclopentyidi(meth)acrylate,tricyclodecyl(meth)acrylate, bicyclopentenyl(meth)acrylate,norbornyl(meth)acrylate, bicyclooctyl(meth)acrylate,tricycloheptyl(meth)acrylate, and cholesterol skeleton-substituted(meth)acrylate; di(meth)acrylates of hydrogenated bisphenols such ashydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenatedbisphenol S, di(meth)acrylates of hydrogenated trisphenols such ashydrogenated trisphenols and di(meth)acrylates of hydrogenatedp,p′-bisphenols; polyfunctional (meth)acrylates having cyclic structuressuch as dicyclopentane type di(meth)acrylate such as “Kayarad R684”(available from Nihon Kayaku Co., Japan), tricyclodecanedimethyloldi(meth)acrylate, bisphenolfluorene dihydroxy(meth)acrylate;and alicyclic acrylates having oxygen atoms and/or nitrogen atoms suchas tetrahydrofurfuryl(meth)acrylate, and morpholinoethyl(meth)acrylate.

[0076] As compounds having acryloyl groups or methacryloyl groups whichcan be used together in the active energy curable composition of thepresent invention, it is possible to use, beside the above recitedcompounds, for example, poly(meth)acryl(meth)acrylates such as areaction product of (meth)acrylic acid polymer andglycidyl(meth)acrylate, and a reaction product of glycidyl(meth)acrylatepolymer and (meth)acrylic acid; (meth)acrylate having amino groups suchas dimethylaminoethyl(meth)acrylate; isocyanul(meth)acrylates such astris((meth)acryloxyethyl)isocyanurate; phosphagene(meth)acrylate such ashexakis [(meth)acryloyloxyethyl)cyclotriphosphagen]; (meth)acrylatehaving the skeleton of polysiloxane; polybutadiene(meth)acrylate; andmelamine(meth)acrylate. Among these compounds having acryloyl ormethacryloyl groups, it is preferable to use the compounds having 1 to 6acryloyl or methacryloyl groups.

[0077] (Meth)acrylamide derivatives, which can be used together in theactive energy curable composition of the present invention, include, forexample, monofunctional (meth)acrylamides such asN-isopropyl(meth)acrylamide and polyfunctional (meth)acrylamides such asmethylenebis(meth)acrylamide.

[0078] Compounds having vinyl ether groups which can be used together inthe active energy curable composition of the present invention can beclassified into, but are not limited to, the following groups, in which:an alkyl vinyl ether having a terminal group substituted with at leastone selected from the group consisting of a hydrogen atom, a halogenatom, a hydroxyl group, and an amino group; a cycloalkyl vinyl etherhaving a terminal group substituted with at least one selected from thegroup consisting of a hydrogen atom, a halogen atom, a hydroxyl groupand an amino group; at least one vinyl ether selected from the groupconsisting of a monovinyl ether, a divinyl ether, and a polyvinyl etherin which a vinyl ether group is connected with alkylene group; and inwhich a vinyl ether group is connected with at least one group with andwithout substituent selected from the group consisting of alkyl group,cycloalkyl group, and aromatic group, via at least one linkage selectedfrom the group consisting of an ether linkage, an urethane linkage, andan ester linkage.

[0079] Alkylvinyl ethers which can be used together in the active energycurable composition includes, for example, but are not limited to,methyl vinyl ether, hydroxymethyl vinyl ether, chloromethyl vinyl ether,ethyl vinyl ether, 2-hydroxyethylvinylether, 2-chloroethylvinylether,diethyl aminoethyl vinyl ether, propyl vinyl ether, 3-hydroxypropylvinyl ether, 2-hydroxpropyl vinyl ether, 3-chloropropyl vinyl ether,3-aminopropyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether,4-hydroxybutyl vinyl ether, isobutyl vinyl ether, 4-aminobutyl vinylether, pentyl vinyl ether, isopentyl vinyl ether, hexyl vinyl ether,1,6-hexanediol monovinyl ether, heptyl vinyl ether, 2-ethlhexyl vinylether, octyl vinyl ether, isooctyl vinyl ether, nonyl vinyl ether,isononyl vinyl ether, decyl vinyl ether, isodecyl vinyl ether, dodecylvinyl ether, isododecyl vinyl ether, tridecyl vinyl ether, isotridecylvinyl ether, pentadecyl vinyl ether, isopentadecyl vinyl ether,hexadecyl vinyl ether, octadecyl vinyl ether, methylene glycol divinylether, ethylene glycol divinyl ether, propylene glycol divinyl ether,1,4-butanediol divinyl ether, 1, 6-hexanediol divinyl ether,cyclohexanediol divinyl ether, trimethylolpropane trivinyl ether,pentaerythritol tetravinyl ether and hexanedioic acid,bis{4-ethenyloxy)butyl} ester.

[0080] Cycloalkyl vinyl ethers which can be used together in the activeenergy curable composition of the present invention includes, forexample, but are not limited to, cyclopropyl vinyl ether,2-hydroxycyclopropyl vinyl ether, 2-chlorocyclopropyl vinyl ether,cyclopropylmethyl vinyl ether, cyclobutyl vinyl ether,3-hydroxycyclobutyl vinyl ether, 3-chlorocyclobutyl vinyl ether,cyclobutylmethyl vinyl ether, cyclopentyl vinyl ether,3-hydroxycyclopentyl vinyl ether, 3-chlorocyclopentyl vinyl ether,cyclopentylmethyl vinyl ether, cyclohexyl vinyl ether,4-hydroxcyclohexyl vinyl ether, cyclohexylmethyl vinyl ether,4-aminocyclohexyl vinyl ether, cyclohexanediol monovinyl ether,cyclohexanedimethanol monovinyl ether, and cyclohexanedimethanol divinylether.

[0081] Among compounds which may be used together in the active energycurable composition of the present invention including monovinyl ether,divinyl ethers, and polyvinyl ethers, in which the vinyl ether linkageconnects with an alkylene group and at least one group selected from agroup consisting of a C₂-C₂₄ alkyl group, a C₂-C₂₄ alicyclic group and aC₂-C₂₄ aromatic group which may have a substituent connects with alinkage selected from a linkage consisting of an ether linkage, anurethane linkage, and an ester linkage, examples of the compoundscontaining an ether linkage, for example, but are not limited to,ethylene glycol methyl vinyl ether, diethylene glycol monovinyl ether,diethylene glycol methylvinyl ether, diethylene glycol divinyl ether,triethylene glycol monovinyl ether, triethylene glycol methylvinylether, triethylene glycol divinyl ether, polyethylene glycol monovinylether, polyethylene glycol methylvinyl ether, polyethylene glycoldivinyl ether, propylene glycol methylvinyl ether, dipropylene glycolmonovinyl ether, dipropylene glycol methylvinyl ether, dipropyleneglycol divinyl ether, tripropylene glycol monovinyl ether, tripropyleneglycol methylvinyl ether, tripropylene glycol divinyl ether,polypropylene glycol monovinyl ether, polypropylene glycol methylvinylether, polypropylene glycol divinyl ether, tetramethylene glycolmethylvinyl ether, di(tetramethylene glycol)monovinyl ether,di(tetramethylene glycol) methyl vinyl ether, di(tetramethylene glycol)divinyl ether, tri(tetramethylene glycol)monovinyl ether,tri(tetramethylene glycol) methylvinyl ether, tri(tetramethyleneglycol)divinyl ether, poly(tetramethylene glycol)monovinyl ether,poly(tetramethylene glycol) methylvinyl ether, poly(tetramethyleneglycol) divinyl ether, 1,6-hexanediolmethyl vinyl ether,di(hexamethylene glycol)monovinyl ether, di(hexamethyleneglycol)methylvinyl ether, di(hexamethylene glycol) divinyl ether,tri(hexamethylene glycol)monovinyl ether, tri(hexamethyleneglycol)methylvinyl ether, tri(hexamethylene glycol) divinyl ether,poly(hexamethylene glycol)monovinyl ether, poly(hexamethylene glycol)methylvinyl ether, poly(hexamethylene glycol) divinyl ether.

[0082] Among compounds classified in the above having vinyl etherlinkages, the compounds having urethane linkage may be obtained by theurethanating reaction between a monovinyl ether of (poly)alkylene glycolhaving at least one hydroxyl group in one molecule and a compound havingat least one isocyanate group in one molecule. Among these compounds,the monovinyl ether of (poly)alkylene glycol include at least onehydroxyl group in a molecule, for example, 2-hydroxyethyl vinyl ether,diethylene glycol monovinyl ether, polyethylene glycol monovinyl ether,3-hydroxpropryl vinyl ether, 2-hydroxy-2-methylethyl vinyl ether,dipropylene glycol monovinyl ether, polypropylene glycol monovinylether, 4-hydroxybutyl vinyl ether, and 1,6-hexanediol monovinyl ether.

[0083] On the other hand, compounds having at least one isocyanate groupin one molecule include, for example, aromatic diisocyanates such asm-isopropenyl-α, α-dimethylbenzylisocyanate, p-phenylenediisocyanate,m-phenylenediisocyanate, p-xylenediisocyanate, m-xylenediisocyanate,2,4-toluenediisocyanate, 2,6-toluenediisocyanate, 4,4′diphenylmethanediioscyanate, 3,3′-diethlydiphenyl-4,4′diisocyanante,3, 3′-dimethyldiphenyl, 4,4′-diisocyanate, naphthalenediisocyanate; andaliphatic and alicyclic isocyanates such as propylisocyanate,isophoronediisocyanate, hexamethylenediisocyanate,4,4′dicylohexylmethanediisocyanate, hydrogenated xylenediisocyanate,norbornenediisocyanate, lysindiisocyanate.

[0084] It is also possible to use isocyanate compounds such as dimers ortrimers comprising more than one of these isocyanate monomers, and touse adduct compounds obtained by urethanating reactions betweenisocyanate compounds containing more than 2 isocyanate groups in onemolecule and various alcohols.

[0085] Various alcohols can be used for obtaining adduct products, ifthe alcohol contains at least one hydroxyl group. Although there is nolimitation, it is preferable to use an alcohol with an average molecularweight of less than 100,000. Examples of such alcohols include, forexample, methanol, ethanol, propanol, isopropanol, butanol, isobutanol,ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, diethyleneglycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol,1,4-butanediol, 1,6-hexanediol, 1,9-nonanediiol, 1,10-decanediol,2,2′,4-trimethyl-1,3-pentanediol, 3-methyl-1,5-pentanediol,dicholoroneopentyl glycol, dibromoneopentyl glycol, neopentylglycolhydroxypivalate, cyclohexanendimethylol, 1,4-cyclohexanediol, spiroglycol, tricyclodecanedimethylol, hydrogenated bisphenol A, ethyleneoxide-modified bisphenol A, propylene oxide modified bisphenol A,dimethylol propionic acid, dimethylol butanoic acid, trimethylol ethane,trimethylolpropane, glycerin, 3-methyl-pentane-1,3,5-triol,tris(2-hydroxyethyl)isocyanurate. Polyester-polyols, polyether-polyols,polycarbonate-polyols may be used for obtaining adduct products. Thesealcohols can be used alone r in combinations of two or more.

[0086] Polyester-polyols obtained by reactions of the above polyolcomponents and carboxylic acids may be used in preparing the adductproducts. In regards to carboxylic acids, any conventional carboxylicacids or anhydrides thereof may be used. Examples of these carboxylicacids include, for example, maleic acid, fumaric acid, itaconic acid,citraconic acid, tetrahydrophthalic acid, hettic acid, chlorendick acid,dimeric acid, adipic acid, succinic acid, alkenylsuccinic acid, sebacicacid, azelaic acid, 2,2,4-trimethyladipic acid,1,4-cyclohexanediacarboxylic acid, terephthalic acid,2-sodiumsulfoterephthalic acid, 2-potassiumsulfoterephthalic acid,isophthalic acid, 5-sodiumsulfoisphthalic acid,5-potassiumsulfoisophthalic acid; di-lower alkylester of5-sodium-sulfoisophthalic acid such as dimethyl-or diethylesters of5-sodium-sulfoisophthalic acid; orthophthalic acid, 4-sulfophthalicacid, 1,10-decamethylenecarboxylic acid, muconic acid, oxalic acid,malonic acid, glutaric acid, trimellitic acid, hexahydrophthalic acid,tetrabromophthalic acid, methylcyclohexenetricarboxylic acid orpyromellitic acid, anhydrides thereof and ester compounds of these acidswith alcohols such as methanol and ethanol. It is also possible to uselactone-polyols obtained by the ring-opening reaction betweenε-caprolactam and the above-described polyols.

[0087] In regard to polyether polyols, conventional polyether polyolscan be used in obtaining adduct products. Examples of suchpolyether-polyols are, for example, but are not limited to, etherglycols such as polytetramethylene glycol, propylene oxide-modifiedpolytetramethylene glycol, ethylene oxide-modified polytetramethyleneglycol, polypropylene glycol, polyethylene glycol, and polyether polyolsobtained by ring-opening reactions of cyclic ethers by use of more thanthree functional polyols as an initiator.

[0088] Polycarbonate polyols used in adduct products are obtained by thetransesterification reactions of carbonates and various polyols.Examples of carbonates are, for example, but are not limited to,diphenylcarbonate, bischlorophenyl-carbonate, dinaphtylcarbonate,phenyl-tolyl-carbonate, phenyl-chlorophenyl-carbonate, and2-tolyl-4-tolyl-carbonate; diaryl-or dialkyl-carbonates such asdimethylcarbonate and diethylcarbonate. Examples of polyols, which canbe used in the above reaction, include the alcohols, polyols, polyesterpolyols, and polyether polyols described above.

[0089] Compounds having ester linkages classified in vinyl ether groupscan be obtained by the esterification reaction of monovinyl ether ofalkylene glycol having at least one hydroxyl group in a molecule with acompound having at least one carboxyl group in a molecule.

[0090] Examples of monovinyl ether of alkylene glycol having at leastone hydroxyl group in a molecule are the same compounds as recited ascomponents of the above compounds having urethane bonds.

[0091] It is possible to use well-known carboxylic acids and anhydridethereof for the compounds having at least one carboxyl group in amolecule. Examples of the compound having at least one carboxyl group ina molecule include, for example, but are not limited to, formic acid,acetic acid, propionic acid, valeic acid, benzoic acid, maleic acid,fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid,hettic acid, chlorendic acid, dimeric acid, adipic acid, succinic acid,alkenylsuccinic acid, sebacic acid, azelaic acid, 2,2′4-trimethyladipicacid, 1,4-cyclohexanedicarboxyl acid, terephthalic acid,2-sodiumsulfoterephthalic acid, 2-potassiumsulfoterephthalic acid,isophthalic acid, 5-sodium-sulfoisophthalic acid,5-potassiumsulfoisophthalic acid, di-lower-alkylesters of5-sodium-sulfoisophthalic acid such as dimethyl-or diethylesters of5-sodium-sulfoisophthalic acid, orthophthalic acid, 4-sulfophtalic acid,1,10-decam thylenedicaboxylic acid, muconic acid, oxalic acid, malonicacid, glutaric acid, trimellitic acid, hexahydrophthalic acid,tetrabromophthalic acid, methylcyclohexenetricarboxylic acid orpyromellitic acid, and anhydrides of these compounds. In addition,carboxyl acids obtained by reactions between compounds having more thantwo carboxylic groups and various alcohols, which are used as componentamong compounds having urethane linkages, and which is used in obtainingadduct products of isocyanate.

[0092] Vinyl carboxylate derivates, which can be, used together in theactive energy curable compositions include, for example, vinyl acetateand vinyl cinnamate. Styrene derivatives include, for example, styreneand divinylstyrene.

[0093] Unsaturated polyester which can be used together in the activeenergy curable composition include, for example, maleates such asdimethylmaleate and diethylmaleate; fumarates such as dimethylfumarateand diethylfumarate; and esterification products of unsaturatedpolycarboxylic acids such as maleic acid and fumaric acid and polyhydricalcohols.

[0094] Unlimited combinations of one or more of any compounds can beused, without being limited to the compounds described herein before andthose represented by general Formula (1) as curable compounds which canbe used together in the active energy curable composition of the presentinvention. However, the compounds must copolymerizable with themaleimide derivates described herein.

[0095] The phrase “water compatible” is used herein to describecompounds that are partially or substantially water dilutable, watersoluble and/or capable of forming a water emulsion or dispersion withthe energy curable composition herein.

[0096] However, in the case where the energy curable compositions areused to formulate coatings, it is preferred that the particular watercompatible compound be compatible with both the water and maleimidederivates in order to avoid any phase separation or precipitation of oneor more of the components. While not wishing to be bound by theory, thewater compatible resin compounds used for coating applications work bestif they possess functional groups which are compatible with water on onehand and functional groups which are compatible with the maleimidederivatives on the other.

[0097] Although there is no particular limitation in the ratio ofmaleimide derivatives represented by Formula (1) to those maleimidederivatives when both maleimide derivatives are used together are usedtogether in the active energy curable composition containing maleimidederivates, it is preferable to select the ratio of maleimide derivativesother than these represented by Formula (1) equal or less than 95% byweight and more preferably equal or less than 90% by weight.

[0098] Although there is no limitation in the ratio of a compound havingacryloyloxy or methacryloyloxy groups to the maleimide derivativesrepresented by Formula (1), when used in the active energy curablecomposition of the present Invention containing maleimide derivates, itis preferable to use the compound having acryloyloxy or methacryloyloxygroups such that 100 parts by weight of the compounds having acryloyloxyor methacryloyloxy groups constitutes a ratio of equal or more than 5parts by weight of maleimide derivatives represented by formula (1),and, more preferably, the ratio of equal or more than 20 parts by weightfrom the point of view of the curing speed.

[0099] When a compound having vinyl ether groups is used together in theactive energy curable composition containing maleimide derivatives ofthe present invention, there is no limitation on the ratio to beincorporated in the composition. However, it is preferable to use thecompound having vinyl ether groups such that 100 parts by weight of thecompound having vinyl ether groups constitutes a ratio of equal or morethan 5 parts by weight of maleimide derivatives represented by Formula(1), and the use of equimolar amount of a vinyl ether group to amaleimide group is more preferable from points of view of the curingspeed and a cured film property.

[0100] The active energy curable compositions of the present inventionhave intrinsic spectral sensitivity ranging from 200 to 400 nm, and itis possible to polymerize same under an irradiation f ultraviolet orvisible light within a range of 180 to 500 nm, even without use of aphotoinitiator. It was observed that lights having wavelengths at 254nm, 308 nm, 313 nm, and 365 nm are effective in curing of the activeenergy curable composition of the present invention. It is also possibleto cure or polymerize the present active energy curable composition bylight other than the ultraviolet light and by heat. In addition, it ispossible to cure the present active energy curable composition in airand/or an inert gas. Various energy cure sources such as thermal,ultraviolet light, infrared and visible light may be used, for example,a low-pressure-mercury lamp, a high-pressure-mercury lamp, an ultrahighpressure-mercury lamp, a metal halide lamp, a chemical lamp, ablack-light lamp, a mercury xenon lamp, an excimer lamp, a short-arclamp, a helium-cadmium laser, an argon laser, an excimer laser andsunlight.

[0101] Although the active energy curable compositions of the presentinvention can be cured under irradiation of ultraviolet light or visiblelight, in the absence of a photoinitiator, conventional photoinitiatorsmay nonetheless be used for polymerization. The photoinitiators may beclassified into two groups; one is an intramolecular-bond-cleavage typeand the other is an intramolecular-hydrogen-abstraction type.

[0102] Examples of the intramolecular-bond-cleavage type photoinitiatorsinclude, for example, acetophenones such as diethoxyacetophenone,2-hydroxy-2-methyl-1-phenylpropane-1-one, benzyldimethylketal,1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one,4-(2-hydroxylethoxy)phenyl-2-hydroxy-2-methylpropyl)ketone,4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone,1-hydroxycyclohexyl-phenylketone,2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, and2-benzyl-2-dimethylamino-144-morpholinophenyl)-butanone; benzoins suchas benzoin, benzoinmethyl ether, benzoinisopropyl ether; acylphosphineoxides such as 2,4,6-trimethylbenzoindiphenylphosphine oxides; benzyland methylphenyl-glyoxyester.

[0103] Examples of intramolecular-hydrogen abstraction typephotoinitiators include, for example, benzophenones such as benzophenonemethyl-4-phenylbenzophenone o-benzoylbenzoate, 4,4′dichlorobenzophenone, hydroxybenzophenone,4-benzoyl-4′-methyl-diphenysulfide, acrylic-benzophenone, 3,3′,4,4′-tetra(t-butylperoxycarbonyl)benzophenone,3,3′-dimethyl-4-methoxybenzophenone; thioxanthones such as2-isopropyl-thioxanthone, 2,4-dimethylthioxanthone,2,4-diethyl-thioxanthone, 2,4-dichlorothioxanthone; aminobenzophenonessuch as Michler's ketone, 4, 4′-diethylaminobenzophenone;10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10phenanthrenequinone and camphorquinone.

[0104] It is preferable to add the photoinitiator to the active energycurable composition within a range of 0.01 to 10.00% by weight.

[0105] Although the active energy compositions of the present inventioncan be cured by irradiation of ultraviolet, it is also possible to use asensitizer for efficient curing.

[0106] Examples of such sensitizer are, for example, amines such astriethanolamine, methyldiethanolamine, triisopropanolamine, methyl4-dimethylaminobenzoate, ethyl 4-dimethyl-aminobenzoate, isoamyl4-dimethylaminobenzoate, (2-dimethyl-amino)ethyl benzoate, (n-butyoxy)ethyl 4-dimethylaminobenzoate, and 2-ethylhexyl 4-dimethylaminobenzoate.It is preferable to add the sensitizer to the active energy curablecomposition within a range of 0.01 to 10.00% by weight.

[0107] It is possible to further use together, if necessary additivessuch as non-reactive compounds, inorganic fillers, organic fillers,coupling reagents, adhesive reagents, antifoaming reagent, levelingreagents, plasticizers, antioxidants, ultraviolet-absorbers, flameretardants, pigments, dyes and paints.

[0108] Examples of the non-reactive compounds which are usable togetherin the active energy curable composition include, for example, but arenot limited to, liquid or solid oligomers or resins with a lowreactivity or non-reactivities such as, alkyl(meth)acrylate copolymer,epoxy resins, liquid polybutadiene, liquid polybutadiene derivatives,liquid chloroprene, liquid polypentadiene, dichloropentadienederivative, saturated polyester oligomer, polyether oligomer, acrylicoligomer, liquid polyamide, polyisocyanate oligomer, xylene resin,acrylic resin, ketone resin, petroleum resin, rosin resin,fluorinate-type oligomer, silicone type oligomer polysulfide oligomers.

[0109] Inorganic and organic fillers are generally used for improvingmechanical properties such as strength, cushioning and slippingproperties.

[0110] Any conventional fillers may be used if the fillers arecompatible with the water containing composition and do not harm thecharacteristics of the resin including curing. Inorganic fillers whichmaybe use used include, for example but are not limited to, siliconedioxide silicon oxide, calcium, carbonate, calcium silicate, magnesiumcarbonate, magnesium oxide, talc, kaoline clay, calcined clay, zincoxide, zinc sulfate, aluminum hydroxide, aluminum oxide, glass, mica,barium sulfate, alumina white, zeolite, silica spherules, and glassspherules. It is possible to add halogen groups, epoxy groups, hydroxylgroups and thiol groups to these fillers by addition or by the reactionwith various coupling reagents such as a silane coupling reagent, atitanate-type coupling reagent, an aluminum-type coupling reagent, azirconate-type couple reagent, and the like.

[0111] Conventional organic fillers which may be used include forexample, but are not limited to, a benzoguanamine resin, a siliconeresin, a low-density polyethylene, a high-density polyethylene, apolyolefin resin, ethylene-acrylate copolymer, polystyrene, crosslinking polystyrene, polydivinylbenzene, styrene-divinylbenzenecopolymer, acrylic copolymer, cross-linking acrylic resin,polymethylmethacrylate resin, vinylidene-chloride resin, fluororesin,nylon 12, nylon 11, nylon 6/66, phenolic resin, epoxy resin, urethaneresin, and polyimide resin. It is possible to add halogen groups, epoxygroups, hydroxyl groups and thiol group to these organic fillers.

[0112] Example of coupling reagents which can be used together in theactive energy curable composition of the present invention include, forexample, but are not limited to, silane coupling reagents suchγ-glycidoxypropyltrimethoxysilane, and γ-chloropropyltrimethoxysilane,titanate coupling reagents such as tetra(2,2-diarloxymethyl-1-butyl)bis(ditridecyl) phosphitetitanate, and bis(dioctylpyrophophate)ethylenetitanate; aluminum coupling reagents such asacetoalkoxyaluminumdiiosopropylate, zirconium coupling agents such asacethylacetone-zirconium complex and the like.

[0113] Regarding additives such adhesive reagents, antifoaming reagents,leveling reagents, flow reagents, plasticizers, antioxidants,ultraviolet-absorbers, flame retardants, pigments, dyes, and paints, anycorresponding conventional additives may be used together, without anylimitation, in the active energy curable composition of the presentinvention, if the additives are compatible with the water containingcomposition and do not harm the characteristics of the resin includingthe curing property.

[0114] In order to obtain the active energy curable composition of thepresent invention, the aforementioned components may be mixed, themixing order or mixing method are not limited.

[0115] It is substantially not necessary to use a solvent in the activeenergy curable composition of the present invention. However, fordiluting the active energy curable composition of the present invention,it may possible to use conventional and generally known solventsincluding ketones such as methylethylketone and methylisobutylketone;acetates such as ethyl acetate and butyl acetate, aromatic hydrocarbonssuch as benzene, toluene and xylene; and alcohols such as methanol,ethanol, isopropyl alcohol, butanol and water.

[0116] The active energy curable composition of the present invention isadvantageously applicable for surface finishing, binders, plasticmaterials, molding materials, laminate plates, adhesives, bondingmaterials, and ink; coating materials for metals such as aluminum, ironand copper; coating materials for plastics such as vinyl chloride,acryls, polycarbonate, polyethyleneterephthalate, andacrylonitrilebutadienestyrene copolymer, polyethylene, andpolypropylene; coating materials for ceramics such as glass; coatingmaterials for other material such as wood, paper, printing paper andfibers.

[0117] The active energy curable composition of the present inventionforms a cured film without a photoinitiator under irradiation of light.Since this active energy curable composition of the present inventiondoes not general odor during curing and the cured film of thiscomposition does not incur yellowing and odor, and an amount of elutionfrom this cured film is quite low, the present composition can beadvantageously applied to a field of inks such as lithographic ink,flexo-ink, gravure ink and screen ink and to fields of gloss varnish,paper coating wood painting, beverage can coating, printing, softpackage coating, adhesives for printed papers and laminates, lavelcoating, printing ink or adhesives, thermosensible paper, printing inkor coating for thermosensible paper, food package coating, printing ink,adhesives and binders, which are directly contacted with a consumer.

[0118] The following examples illustrates specific aspects of thepresent invention and are not intended to limit the scope thereof in anyrespect and should not be so construed. In the examples, all parts areby weight unless otherwise indicated. The relationship of parts byweight to parts by volume is as that of kilograms to liters.

[0119] In the examples, the energy curable compositions were coated onopacity charts (uncoated Leneta N2A, available from Leneta Corporation,Mahwah, N.J.) using a #3 Mayer rod having a thickness of 7.5 microns.The ultraviolet radiation energy cure source was provided using aconveyor type unit with a medium pressure mercury lamp of variable lightintensities (e.g. 120, 200, 300 watts per inch (wpi) available fromFusion Aetek, Rockville Md.) at conveyor speeds varying from 100 to 200feet per minute (fpm). At 200 wpi and 100 fpm the ultraviolet exposuredose was 228 mJ/cm², measured using a radiometer (UV Power Puck, PowerPuck is a Registered Trademark of EIT Incorporated, VA). This dose isnormally sufficient to produce a commercially viable film. The surfaceharness of the coating was empirically measured by scratching thesurface with a human nail. The reflective gloss of the cured film wasmeasured at 600 using a glossmeter (Micro-Gloss 60, available fromBYK-Gardner Incorporated, MD). The solvent resistance of the cured filmwas measured by the surface with a cotton tipped applicator soaked inmethyl ethyl ketone (MEK), isopropyl alcohol or water until thesubstrate was exposed. The number of rubs, i.e. one stroke back andforth across a surface, were recorded. A coating exhibiting 10 rub MEKresistance, for example, was considered to be commercially feasible.

EXAMPLE 1 Synthesis Example

[0120] Glycine (37.5 g) and acetic acid (400 ml) were admixed then asolution of maleic anhydride (49.0 g) and acetic acid (300 ml) was addeddropwise over 2 hours under stirring. The reaction was continued for 1hour and the precipitate that formed was filtered off and recrystallizedfrom a 70% aqueous methanol solution. To this product (102 g),triethylamine (40.4 g), and toluene (500 ml) were added and the mixturewas reacted for 1 hour while stirring under reflux to remove the evolvedwater. The residue, obtained by removing toluene from the reactionmixture, was acidified to a pH of 2 with 0.1 N HCl, extracted 3 timeswith ethyl acetate (100 ml) and dried with magnesium sulfate. The ethylacetate was then evaporated under pressure and the residue wasrecrystallized from water, whereby pale yellow crystals ofmaleimidoacetic acid (11 g) were obtained. ¹H NMR (300 MHz, DMSO-d6):7.0 ppm (s, 2H, —C═C—); 4.1 ppm (s, 2H, —CH2—); IR: 3170 cm⁻¹ (—COOH);1750 cm⁻¹; 1719 cm⁻¹ (C═O); 831 cm⁻¹; 696 cm⁻¹ (—C═C—); Elementalanalysis (CHN): Calcd. C:46.5%; H:3.87%; N:9.03%; Found C:46.2%;H:4.05%; and N:8.70%.

[0121] Maleimidoacetic acid (6.8 g), polytetramethylene glycol (10 g, MWof 250, tradename PolyTHF 250, available from BASF Corporation, Japan),p-toluenesulfonic acid (1.2 g), 2,6-tert-butyl-p-cresol (0.06 g), andtoluene (15 ml) were added together and reacted at 80° C. for 4 hoursunder reduced pressure (240 torr). The mixture was stirred and the waterformed during the reaction was removed. The reaction mixture was thendissolved in toluene (200 ml) and washed 3 times with a saturated sodiumhydrogen carbonate aqueous solution (100 ml) and a saturated sodiumchloride aqueous solution (100 ml). The toluene was then removed underreduced pressure and a maleimide derivative (16 g) having the structurebelow was obtained.

EXAMPLE 2 Synthesis Examples

[0122] Glycine (37.5 g) and acetic acid (400 ml) were admixed then asolution of maleic anhydride (49.0 g) and acetic acid (300 ml) was addeddropwise over 2 hours under stirring. The reaction was continued for 1hour and the precipitate that formed was filtered off and recrystallizedfrom a 70% aqueous methanol solution. To this product (102 g),triethylamine (40.4 g), and toluene (500 ml) were added and the mixturewas reacted for 1 house while stirring under reflux to remove theevolved water. The residue, obtained by removing toluene from thereaction mixture, was acidified to a pH of 2 with 0.1 N HCl, extracted 3times with ethyl acetate (100 ml) and dried with magnesium sulfate. Theethyl acetate was then evaporated under reduced pressure and the residuewas recrystallized from water, whereby pale yellow crystals ofmaleimidoacetic acid (11 g) were obtained. ¹H NMR (300 MHz, DMSO-d6):7.0 ppm (s, 2H, —C═C—); 4.1 ppm (s, 2H, —CH2—) IR: 3170 cm⁻¹ (—COOH);1750 cm⁻¹; 1719 cm⁻¹ (C═O) 831 cm⁻¹; 696 cm⁻¹ (—C═C—); Elementalanalysis (CHN): Calcd. C:46.5%; H:3.87%; N:9.03%; Found C:46.2%;H:4.05%; and N:8.70%.

[0123] Maleimidoacetic acid (6.8 g) pentaerythritol modified by 4 molesof ethylene oxide (4.1 trade name PNT-40 Mn:490, Mw:530, available fromNippon Emulsifying Agent Co., Ltd., Japan), p-toluenesulfonic acid (1.2g), 2,6-tert-butyl-pcresol (0.06 g), and toluene (15 ml) were addedtogether and reacted at 80° C. for 4 hours under reduced pressure (24015 torr). The mixture was stirred and the water formed during thereaction was removed. The reaction mixture was then dissolved in toluene(200 ml) and washed 3 times with a saturated sodium hydrogen carbonateaqueous solution (100 ml) and a saturated sodium chloride aqueoussolution (100 ml).

[0124] The toluene was then removed under reduced pressure and amaleimide derivative (18 g) having the structure below was obtained

EXAMPLE 3

[0125] An aliphatic epoxy acrylate resin (55 wt. %, Laromer 8765,available from BASF, Mt. Olive, N.J.) was combined with water (8.5 wt.%). Next, a maleimide as prepared in Example 1 (36 wt. %) was added. Apolyether siloxane additive (0.5 wt. %, Glide 440, available from TegoChemie, VA) was then added to produce sufficient flow properties. Thecuring, solvent resistance, gloss and surface hardness properties of thecoating as described above were then evaluated. The results are shown inTable 1.

EXAMPLE 4 Comparative

[0126] The maleimide prepared in Example 1 (84.5 wt. %) was added towater (15 wt. %). A polyether siloxane additive (0.5 wt. %, Glide 440,available from Tego Chemie, VA) was then added to produce sufficientflow properties. The energy curing properties of the coating could notbe evaluated because the water and maleimide were found to beincompatible and no film was produced.

EXAMPLE 5

[0127] An aliphatic epoxy acrylate resin (58 wt. %, Laromer 8765,available from BASF, Mt. Olive, N.J.) was combined with water (13.6 wt.%). Next, a photoinitiator,4-(2hydroxylethoxy)phenyl-(2-Hydroxy-2-methylpropyl) ketone was added (3wt. %, Irgacure 2959, available from Ciba-Geigy, NY). A polysiloxaneadditive (0.4 wt. %, DC57, available from Dow Chemical, Midland, Mich.)was then added to produce sufficient flow properties. Finally, themaleimide prepared in Example 1 (25 wt. %) was then added. The curing,solvent resistance, gloss and surface hardness properties of the coatingdescribed above were then evaluated. The results are shown in Table 1.

EXAMPLE 6

[0128] An aliphatic epoxy acrylate resin (50 wt. %, Laromer 8765,available from BASF, Mt. Olive, N.J.) was combined with water (17 wt.%). The maleimide prepared in Example 1 (17 wt. %, MIA250) was thenadded along with isopropyl alcohol (15.5 wt. %). A polyether siloxaneadditive (0.5 wt. %, Glide 440, available from Tego Chemie, VA) was thenadded to produce sufficient flow properties. The composition wasirradiated at three different doses. The curing, solvent resistance,gloss and surface hardness properties of the coating for each dose asdescribed above were then evaluated. The results are shown in Table 1.

EXAMPLE 7

[0129] A water dilutable aliphatic urethane acrylic resin (25 wt. %,Ebecryl 2001, available from UCB Radcure, Ga.) was combined with water(49.5 wt. %). The maleimide prepared in Example 1 (25 wt. %, MIA 250)was added along with a polyether siloxane additive (0.5 wt. %, Glide 440available from Tego Chemie, VA) to produce sufficient flow properties.The composition was irradiated at two different doses. The curing,solvent resistance, gloss and surface hardness properties of the coatingdescribed above were then evaluated. The results are shown in Table 1.

EXAMPLE 8

[0130] A highly alkoxylated trimethylolpropane triacycrylate resin (61wt. %, SR 9035, available from Sartomer, PA) was combined with water (24wt. %). The maleimide prepared in Example 1 (14.5 wt. %) was added. Apolyether siloxane additive (0.5 wt. %, Glide 440, available from TegoChemie, VA) was then added to produce sufficient flow properties. Thecomposition was irradiated at two different doses. The curing, solventresistance, gloss and surface hardness properties of the coatingdescribed above were then evaluated. The results are shown in Table 1.

EXAMPLE 9

[0131] An aliphatic epoxy acrylate resin (57 wt. %, Laromer 8765,available from BASF, Mt. Olive, N.J.) was combined with water (10.5 wt.%). A vinyl ether, hexanedioic acid, bis(4-ethenyloxy)butylester (10.5wt. %, VEX 4060, available from Allied Signal, NJ) was then added. Amaleimide as prepared in Example 1 (21.5 wt. %) was then added alongwith a polysiloxane additive (0.5 wt./0, DC57, available from DowChemical, Midland, Mich.) to produce sufficient flow properties.

[0132] The composition was irradiated at two different doses. Thecuring, solvent resistance, gloss and surface hardness properties of thecoating described above were then evaluated. The results are shown inTable 1.

EXAMPLE 10 Comparative

[0133] A vinyl ether, hexanedioic acid, bis(4-ethenyloxy)butyl)ester (67wt. %, VEX 4060, available from Allied Signal, NJ) was added to water(11 wt. %). The maleimide prepared in Example 1 (21.5 wt. %), was addedalong with a polyether siloxane additive (0.5 wt. %, DC57, availablefrom Dow Chemical, Midland, Mich.) to produce sufficient flowproperties. The energy curing properties of the coating could not beevaluated because the water and maleimide were found to be incompatibleand no film was formed.

EXAMPLE 11

[0134] An aliphatic epoxy acrylate resin (72 wt. %, Laromer 8765,available from BASF, Mt. Olive, N.J.) was combined with water (16 wt.%). The maleimide prepared in Example 2 (11.2 wt. %, MIA-PE4EO) was thenadded. A polyether siloxane additive (0.8 wt. %, Glide 440, availablefrom Tego Chemie, VA) was then added to produce sufficient flowproperties. The curing, solvent resistance, gloss and surface hardnessproperties of the coating described above were then evaluated. Theresults are shown in Table 1.

EXAMPLE 12 Comparative

[0135] A maleimide prepared in Example 2 (84.5 wt. %, MIA-PE4EO) wasadded to water (15 wt. %). A polyether siloxane additive (0.5 wt. %,Glide 440, available from Tego Chemie, VA) was then added to producesufficient flow properties. The energy curing properties of the coatingcould not be evaluated because the water and maleimide were found to beincompatible and no film was produced. TABLE 1 Cure 60° Solvent SolventRate Surface Gloss Rubs Rubs Example (mJ/cm²) Hardness (%) (MEK) (Water)3 228 Excellent 85-90 65 >200 5 228 Excellent 92 40-44 >200 6 125 Verygood 85-88 8 50 6 209 Very good 88-90 12-15 70 6 254 Excellent 88-9038 >200 7 228 Good 80-82 45 N.A. 7 607 Very good 80-82 75 N.A. 8 204Fair 65-70 3 8 8 305 Good 65-70 5 19 9 228 Very good 86-87 9 31 9 456Excellent 87-88 31 66 11 228 Fair 86 26 80

[0136] The data in Table 1 shows several characteristics of the watercompatible energy curable compositions of the present invention. Thedose required to cure the composition was similar to that used to cureconventional energy curable materials. The surface hardness and gloss ofthe cured films were comparable to commercial coatings usingphotoinitiators. The solvent rubs of the cured compositions were typicalof the results that would be achieved with a similar compositioncontaining commercial photoinitiators and resins. This is by exemplifiedby Example 3 wherein the cure rate doses of 228 mJ/cm² represents aconveyor speed of 100 fpm and 200 wpi lamp intensity, represent acommercially practical amount of energy delivered to cure thecomposition. Examples 3 and 7 depict gloss values greater than 80, whichare indicative of a high commercial grade gloss. Example 3 depictssolvent rubs of 65 with MEK and greater than 200 with water. Thesevalues are typically higher than those shown for conventional commercialcoatings cured under similar conditions. Example 6 shows that bydoubling the curing dose, from 125 to 254 mJ/cm² for the energy curablecompositions of the present invention, one can improve its filmproperties, such as surface hardness, gloss and crosslink density asmeasured by solvent resistance and illustrated by an increase in MEKsolvent rubs from 8 to 38. Example 9 shows a similar increase in solventrubs, from 9 to 31 MEK rubs and 31 to 66 water rubs. Although a highercure rate dose was required, it was still within the range forcommercial curing.

[0137] The present invention has been described in detail, including thepreferred embodiments thereof. However, it will be appreciated thatthose skilled in the art may make numerous variations or modificationsof the embodiments that fall within the scope and spirit of theinvention as set forth in the following claims.

What is claimed:
 1. An actinic radiation curable printing ink or coatingcomprising an active single phase water compatible actinic radiationcurable composition of a water compatible non-emulsion, non-dispersingcompound water, and a maleimide derivative of the formula:

wherein n and m each independently represent an integer of 1 to 5, andthe total of m and n is 6 or smaller; R₁₁ and R₁₂ each independentlyrepresent a linking group selected from the group consisting of analkylene group, an alicyclic group, an arylalkylene group, and acycloalkylalkyene group; G₁ and G₂ each represent an ester linkageselected from the group consisting of —COO and —OCO—; and R₂ representsa linking chain having an average molecular weight of 100 to 100,000selected from the group consisting of a (poly)ether or (poly)esterlinking chain, in which at least one organic group consists of a groupor groups selected from a straight or branched chain alkylene group, analkylene group having a hydroxyl group, an alicyclic group, an arylgroup, an arylalkylene group, and a cycloalkylalkyene group connectedvia at least one linkage selected from the group consisting of an etheror ester linkage.